CN1639265A - Heat ray shielding sheet material and liquid additive for use in producing the same - Google Patents
Heat ray shielding sheet material and liquid additive for use in producing the same Download PDFInfo
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- CN1639265A CN1639265A CNA038054124A CN03805412A CN1639265A CN 1639265 A CN1639265 A CN 1639265A CN A038054124 A CNA038054124 A CN A038054124A CN 03805412 A CN03805412 A CN 03805412A CN 1639265 A CN1639265 A CN 1639265A
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- radiation shielding
- hot radiation
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- hexaboride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
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Abstract
A heat ray shielding sheet material which comprises a polycarbonate resin, an acrylic resin, or the like and, dispersed therein, fine particles of a hexaboride, such as LaB6, as a heat ray shielding component. The heat ray shielding sheet material exhibits a maximum transmissivity in a visible light region, and, in a near infrared region, exhibits strong absorption, and thus, a minimum transmissivity. The sheet material may further comprise ITO fine particles and/or ATO fine particles dispersed therein. The heat ray shielding sheet material can be produced by an easy and simple method, without the use of a complicated production method or a costly physical film formation method, and combines the retention of excellent transmission for a visible light and high shielding capability for a heat ray and is excellent also in mechanical strength properties such as impact strength.
Description
Technical field
The present invention relates to be used for the roof of buildings or wall, arch, top ceiling dome etc. or vehicle window etc. opening portion and visible light permeability is good and hot radiation shielding is good and shock-resistance or water tolerance might as well the hot radiation shielding resin sheet.
Technical background
Always, the said opening portions such as window of various buildingss or vehicle constitute with transparent sheet glass or resin board in order to enter sunlight.Yet the near infrared ray that also contains 800～2500nm in ultraviolet ray and infrared rays, the especially infrared rays in the sunlight except visible light is called hot line, owing to the hot line that enters from opening portion becomes the reason that room temp rises.
Therefore, in recent years,, studying and fully to enter visible light maskable hot line again, and when keeping lightness, can suppress the hot radiation shielding material that room temp rises again, proposing the whole bag of tricks for this reason as the window material of various buildingss or vehicle etc.
For example, the spy opens clear 61-277437 communique and has proposed hot line reflective film that evaporation metal on the transparent resin film is formed, is bonded in the hot radiation shielding plate on the transparent substrate of sheet glass, polyacrylic plate, polycarbonate plate etc.Yet this heat reflection film itself is not only very expensive, and owing to need numerous and diverse operation of bonding process etc., so there is the very high shortcoming of cost.In addition, because the cementability of transparent substrate and heat reflection film is bad, so exist because of changing the problem that the heat reflection film is peeled off that produces in time.
In addition, directly the hot radiation shielding plate that forms of evaporation metal or metal oxide has also proposed many schemes on transparency carrier surface, but need the control environment evaporation coating device of atmosphere of high vacuum or pinpoint accuracy because must use, so exist mass production poor, shortage versatility, the problem that the hot radiation shielding plate is also very expensive.
In addition, present inventors open for example spy that flat 11-181336 communique, spy are opened the 2000-96034 communique, the spy opens in 2000-169765 communique etc., proposed to make the hot radiation shielding coating fluid that contains or hexaboride particulate and ITO particulate and/or ATO particulate independent in the various caking agents as the hexaboride particulate of hot radiation shielding composition, and after being coated on this coating fluid on the transparent substrate surface, make it to solidify the hot radiation shielding film that obtains.
Method as hot radiation shielding, except imposing on the above-mentioned transparent substrate hot line reflective film or the hot radiation shielding film, for example, Te Kaiping 5-78544 communique or spy open in the flat 2-173060 communique, also proposed in the transparent resin of acrylic resin or polycarbonate resin etc., sneaked into as the formed hot radiation shielding plate of mica of hot line reflective particle with the titanium oxide lining.
Yet this hot radiation shielding plate must heavy addition hot line reflective particle in order to improve the hot radiation shielding performance, the problem that exists visible light permeability to reduce when therefore increasing the addition of hot line reflective particle.Otherwise when reducing the addition of hot line reflective particle, therefore the hot radiation shielding reduction though visible light permeability is high is difficult to satisfy simultaneously hot radiation shielding and visible light permeability.In addition, when cooperating the hot line reflective particle in a large number, also have the rerum natura as the transparent resin of base material, especially shock-resistance or toughness reduce the shortcoming of these intensity aspects.
The present invention is in view of in the past situation, its purpose be to provide need not be numerous and diverse method for making or expensive physical film deposition method and adopt easy method to make, the excellent visible light perviousness can be kept and high hot radiation shielding can be brought into play simultaneously, and the hot radiation shielding material of shock-resistance equal strength aspect.
Summary of the invention
In order to achieve the above object, present inventors are conceived to preserve in a large number the hexaboride particulate of unbound electron as the composition that the hot radiation shielding effect is arranged, by making this microparticulate in the transparent resin of polycarbonate resin or acrylic resin etc., developing has great transmitance to visible domain, simultaneously the near infrared territory is presented strong absorption and the hot radiation shielding resin sheet of minimum transmitance is arranged, thereby finished the present invention.
That is, hot radiation shielding resin sheet provided by the invention is characterized in that in transparent resin base material, disperses the hexaboride particulate as the hot radiation shielding composition, perhaps disperses hexaboride particulate and ITO particulate and/or ATO particulate.
In the hot radiation shielding resin sheet of the invention described above, aforementioned hexaboride particularly, is preferably selected from LaB
6, CeB
6, PrB
6, NdB
6, GdB
6, TbB
6, DyB
6, HoB
6, YB
6, SmB
6, EuB
6, ErB
6, TmB
6, YbB
6, LuB
6, SrB
6And CaB
6In at least a kind.In addition, aforementioned hexaboride particulate, ITO particulate and ATO particulate, its median size is 200nm or below the 200nm preferably all.
In addition, in the hot radiation shielding resin sheet of the invention described above, the amount of aforementioned hot radiation shielding composition, every 1m
2The hot radiation shielding resin sheet preferably contains 0.05～19g.The ratio of aforementioned hexaboride particulate and ITO particulate and/or ATO particulate, 0.1: 99.9～90: 10 scope preferably by weight.In addition, preferably polycarbonate resin or acrylic resin of aforementioned resin base material.
The hot radiation shielding resin sheet of the invention described above can form the resin coating that contains UV light absorber at least one surface of this hot radiation shielding resin sheet.
The present invention also is provided for making the annex solution of above-mentioned hot radiation shielding resin sheet.Promptly, hot radiation shielding resin sheet manufacturing annex solution of the present invention, it is the annex solution that is mixed and made into hot radiation shielding resin sheet molding composition with resin or resin raw material, it is characterized in that, in solvent, disperse hexaboride particulate, or disperse hexaboride particulate and ITO particulate and/or ATO particulate as the hot radiation shielding composition.
The hot radiation shielding resin sheet manufacturing of the invention described above is with in the annex solution, and aforementioned hexaboride preferably is selected from LaB
6, CeB
6, PrB
6, NdB
6, GdB
6, TbB
6, DyB
6, HoB
6, YB
6, SmB
6, EuB
6, ErB
6, TmB
6, YbB
6, LuB
6, SrB
6, and CaB
6In at least a kind.
In addition, the hot radiation shielding resin sheet manufacturing of the invention described above is with in the annex solution, aforementioned hexaboride particulate, ITO particulate and ATO particulate, and its median size is 200nm or below the 200nm preferably all.In addition, the ratio of aforementioned hexaboride particulate and ITO particulate and/or ATO particulate, 0.1: 99.9～90: 10 scope preferably by weight.
The preferred plan that carries out an invention
Hot radiation shielding resin sheet of the present invention; be in the transparent resin base material of polycarbonate resin or acrylic resin and so on; disperse hexaboride particulate separately as the hot radiation shielding composition; or make up with the hexaboride particulate and to disperse ITO particulate or ATO particulate, and can be processed into shape arbitrarily such as tabular, film like, dome shape according to purposes.
The manufacture method of such hot radiation shielding resin sheet is so long as the method that the particulate of hot radiation shielding composition can be dispersed in the resin just can at random be selected for use.For example, can adopt above-mentioned particulate is directly added in the resin, carry out the method for melting mixing equably.Especially, preparation makes the annex solution of microparticulate in solvent of hot radiation shielding composition, and use is simple and preferred with this annex solution mixes the molding composition moulding resin sheet that obtains with resin or resin raw material method.
As hexaboride particulate, can enumerate lanthanum hexaborane (LaB as the hot radiation shielding composition
6), six cerium boride (CeB
6), praseodymium boride (PrB
6), neodymium hexaboride (NdB
6), six boronation gadolinium (GdB
6), six terbium boride (TbB
6), six dysprosium boride (DyB
6), six boronation holmium (HoB
6), six yttrium boride (YB
6), six samarium boride (SmB
6), europium boride (EuB
6), six boronation erbiums (Er), six thulium boride (TmB
6), six ytterbium boride (YbB
6), six boronation lutetium (LuB
6), six strontium boride (SrB
6), six calcium boride (CaB
6), lanthanum hexaborane cerium ((La.Ce) B)
6) wait as representative hexaboride.
In addition, employed hexaboride particulate, the preferably not oxidation of surface of this particle, but common great majority low-level oxidation slightly, and in the microparticulate operation, unavoidably cause the oxidation on surface in a way, but that present the validity of hot radiation shielding effect this moment is constant.In addition, boride microparticle is got over Gao Zeyue as the crystalline thoroughness and is obtained big hot radiation shielding effect, even the low this occasion that adopts X-ray diffraction to produce wide diffraction peak of crystallinity, the basic combination of particulate inside is so long as the occasion that is made of metal and combining of boron just can present the hot radiation shielding effect.
These hexaboride particulate is the powder that is coloured to grey black, tea black, green black etc., and with than under the very little state of particle size dispersion in resin sheet of visible wavelength, not only keep sufficiently high infrared light shielding, and resin sheet can obtain the visible rays perviousness.This reason does not also have at length to be understood, but the amount of thinking the unbound electron in these particulates is many, because the absorption of the indirect migration of the energy interband that particulate is inner and surperficial unbound electron causes can be in from visible domain near the near infrared light territory, therefore optionally reflect, absorb the hot line of this wavelength domain.
Particularly, very thin and homodisperse has the resin sheet of hexaboride particulate, observing transmitance is having maximum value and between wavelength 700nm～1800nm mnm. is being arranged between wavelength 400nm～700nm, the difference of the maximum value of these transmitances and mnm. is 15 percentage points (15 Port イ Application ト) or more than 15 percentage points again.If considering visible wavelength is 380nm～780nm, the visual sense degree be near the 550nm for peak value hang bell the time, find that the resin sheet that is dispersed with the hexaboride particle sees through visible light effectively, and the hot line beyond the reflection-absorption visible light effectively.
In addition, the ITO particulate or the ATO particulate that are used in combination with the hexaboride particulate almost do not have the absorption or the reflection of light at visible domain, and be big from the reflection-absorption that plasma resonance produces at 1000nm or the field more than the 1000nm.In addition, these see through graphic representation, along with reducing towards long wavelength side, on the other hand, seeing through in the graphic representation of hexaboride has mnm. as mentioned above near 1000nm, therefore present transmitance at long wavelength side and rise gradually near infrared territory transmitance.So be used in combination by hexaboride and ITO or ATO, visible light transmissivity does not reduce, and the hot line in maskable near infrared ray field, to compare with using separately respectively, the hot radiation shielding characteristic improves.
The preferred 200nm of the median size of employed hexaboride particulate or below the 200nm.Median size is during greater than 200nm, and particulate aggegation each other strengthens and becomes the sedimentation reason of particulate in the dispersion liquid, and forming the scattering of light source in resin, that resin sheet is presented is dizzy turbid.The particulate of ITO particulate or ATO particulate is also because preferred median size is 200nm or below the 200nm with above-mentioned same reason.In addition, for the light transmission roof Material etc., require opaque photopermeability rather than the transparency sometimes, this occasion preferably increases the formation that particle diameter encourages scattering, but infrared absorption can itself also decay when particle diameter was too big, so still preferred 200nm or the following median size of 200nm.
The hot radiation shielding ability of hexaboride particulate per unit weight is very high, compares with ITO particulate or ATO particulate, has only the usage quantity below 1/30 or 1/30 just can bring into play equal effect.Therefore, by using the hexaboride particulate, even the few hot radiation shielding effect that also can obtain of amount, and the particulate that can cut down these when using with ITO particulate or ATO particulate reduces cost seeking.In addition, owing to can cut down the usage quantity of whole particulates significantly, reduce so can prevent rerum natura, especially impact strength or flexible as the resin of base material.
In addition, by the amount of the hexaboride particulate of control in the resin sheet, or the amount of the ITO particulate of control and usefulness or ATO particulate, the absorption of visible domain can be freely controlled, also adjusting brightness can be carried out, or the application of secret protection etc.
The hot radiation shielding performance is decided by the amount of the hot radiation shielding composition of per unit area sheet material, but the hot radiation shielding composition is with respect to the amount of resin, must determine according to the strength characteristics of needed optical characteristics or resin sheet etc.For example, even satisfy the hot radiation shielding composition amount of optical characteristics, and resin sheet attenuation time abrasion intensity or shock-resistance also reduce.In addition, produce hot radiation shielding on the resin sheet surface and become to analyze the possibility that disfeatures.Therefore, when resin sheet approaches, when thickness is 20～30 μ m left and right sides particularly, in order not produce above-mentioned bad phenomenon, the preferred every 1m of the amount of hot radiation shielding composition
2Resin sheet is the scope of 0.05～19g.And, when thickening, resin sheet may contain the hot radiation shielding composition more, if the thickness of resin sheet increases to about 3～5mm, hot radiation shielding composition amount surpasses above-mentioned 19g/m
2The time, the possibility that visible light permeability reduces appears.
Ratio when the hexaboride particulate is used with ITO particulate and/or ATO particulate, the hexaboride particulate: the weight ratio of (ITO particulate and/or ATO particulate) is preferably 0.1: 99.9～90: 10 scope.The hexaboride particulate than this scope after a little while, the usage quantity of total particulate does not reduce so that cost reduces effect is not little, the hot radiation shielding characteristic is variation also.And, the hexaboride particulate than this scope for a long time, the additive effect of ITO or ATO little can ignore.In addition, the occasion of same optical properties, the amount of hexaboride particulate is many more, can reduce the usage quantity of ITO particulate and ATO particulate more, and the reduction effect of cost increases.
The dispersing method of hot radiation shielding composition in resin so long as the method that particulate can be dispersed in the resin does not then have particular determination, but preferably uses the method for the annex solution of microparticulate in any solvent.Particularly, for example use the method for ball grinding machine, ball mill, sand mill, ultrasonic dispersing etc., above-mentioned microparticulate is become the annex solution of hot radiation shielding resin sheet manufacturing usefulness in solvent arbitrarily.
Dispersion solvent as the annex solution of hot radiation shielding resin sheet manufacturing usefulness uses does not have particular determination, can form the selections such as condition of resin sheet according to the resin that cooperates, and can use general organic solvent.Can also add acid or alkali as required and regulate pH.In addition, in order further to improve the dispersion stabilization of particulate in the resin, also can be various tensio-active agents, coupling agents etc. add as dispersion agent.
Use above-mentioned annex solution to make the hot radiation shielding resin sheet, the general employing added this annex solution in the resin as base material to, use the mixing machine of ribbon blender, rotary drum, Nuo Ta (Nanta) mixing machine, high speed Henschel mixer, superhigh speed mixing machine, planetary-type mixer etc., the mixing roll that reaches Banbury, kneader, roller refining machine, kneading mixing roll, single screw extrusion machine, twin screw extruder etc. carries out the method for melting mixing equably, and homodisperse the mixture of particulate in the adjustment resin.
Resin as base material is the occasion of polycarbonate resin, and annex solution is added in the dihydric phenols as resin raw material.Adopt known method to mix equably, also can adjust the mixture that homodisperse in the resin particulate by reacting with phosgene and the carbonate precursor enumerated.In addition, the occasion of acrylic resin, annex solution is added in methyl methacrylate as the acrylic resin raw material, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate etc., similarly adopt known method to mix equably, by adopting known method such as suspension polymerization or mass polymerization to carry out polymerization, can adjust the mixture that homodisperse in the acrylic resin particulate.
In addition, adopt known method to remove the solvent of annex solution, the powder that obtains is added in the resin, the method for melting mixing is carried out in employing equably, also can adjust the mixture that homodisperse in the resin particulate.
Resin sheet of the present invention can adopt known forming methods such as injection molding, extrusion moulding, compressed moulding, and the mixture of homodisperse in the aforesaid resin particulate becomes plane by forming process or the curved surface shape is made.In addition, also can use prilling granulator that homodisperse in the resin a granulation of mixture of particulate after, adopt the manufacturing resin sheet that uses the same method.In addition, the thickness of resin sheet can be according to being adjusted to thickness arbitrarily from thick plate-like to laminal requirement.
Surface at above-mentioned resin sheet also can form hot radiation shielding film or ultraviolet radiation absorption film again.For example, also can on resin sheet, be coated with the coating fluid of be scattered here and there in the various caking agents hexaboride particulate or ITO particulate or ATO particulate, form the hot radiation shielding film from the teeth outwards again.In addition, can be on above-mentioned resin sheet, be dissolved with the coating fluid of the UV light absorber of benzotriazole system, benzophenone series etc. in the various caking agents of coating, solidify back formation ultraviolet radiation absorption film.By forming the weathering resistance that this ultraviolet radiation absorption film can improve resin sheet.
In addition, as the polycarbonate resin of the base material of resin sheet, adopting solution method or scorification to make dihydric phenols and carbonic ether is that precursors reaction makes.As dihydric phenol, can enumerate 2, two (4-hydroxy phenyl) propane [dihydroxyphenyl propane], 1 of 2-, two (4-hydroxy phenyl) ethane, 1 of 1-, 1-bis(4-hydroxyphenyl) cyclohexane, 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, 2, two (4-hydroxyl-3, the 5-dibromo phenyl) propane, 2 of 2-, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, two (4-hydroxy phenyl) sulfide, two (4-hydroxy phenyl) sulfone etc. are as typical example.And preferred dihydric phenol is two (4-hydroxy phenyl) paraffinic, and most preferably dihydroxyphenyl propane is the dihydric phenol of main component.
In addition, as acrylic resin, can use methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate to be main raw material, use polymkeric substance or the multipolymer as copolymer composition such as acrylate that C1～C5 alkyl is arranged, vinyl acetate, vinylbenzene, vinyl cyanide, methacrylonitrile as required.Can also use the acrylic resin of multi-stage polymeric.
Like this, there is the hexaboride particulate of strong absorption to be dispersed in the resin by making to the near infrared territory as the hot radiation shielding composition, when forming sheet, physical film deposition method that need not be expensive or numerous and diverse bonding process, have the hot radiation shielding function and can provide, and visible domain is had the hot radiation shielding resin sheet of high-permeability energy.
In addition; the hexaboride particulate used as the hot radiation shielding composition with ATO particulate or ITO particulate be dispersed in hot radiation shielding resin sheet in the resin; can improve the hot radiation shielding characteristic more when using separately various particulate; reduce the usage quantity of ATO or ITO simultaneously than the occasion of an ATO or ITO, thereby can realize the reduction of Master Cost.
In addition, because hexaboride particulate water tolerance is low, be subjected to the influence of water and deterioration, so the shortcoming that exists optical characteristics to change, and the present invention makes the resin sheet of hexaboride microparticulate in resin can intercept contacting of hexaboride particulate and water, so can prevent change of optical property.
Embodiment 1
The LaB of median size 67nm
6Particulate 20g, toluene 70g, water and an amount of dispersion agent mix, and use the zirconia ball of diameter 4mm to carry out ball mill mixing in 100 hours, make annex solution (Al liquid) 100g.In addition, ITO particulate 20g, toluene 70g, water and an amount of dispersion agent of median size 80nm are mixed, similarly carry out ball mill and mix, make annex solution (B1 liquid) 100g.Again, ATO particulate 20g, toluene 70g, water and an amount of dispersion agent of median size 55nm mixed, similarly carry out ball mill and mix, make annex solution (C1 liquid) 100g.
Then, above-mentioned A1 liquid is mixed with B1 liquid, allotment polycarbonate annex solution adds this annex solution to that to make ITO concentration in the polycarbonate resin be 0.155 weight %, LaB
6Concentration is 0.00097 weight %, use mixing roll, twin screw extruder evenly to carry out melting mixing after, uses the T type to get to know to extrude formation thickness to be 3mm, make the whole homodisperse hot radiation shielding polycarbonate sheets of hot radiation shielding particulate (test portion 1).
Adopt and above-mentioned same method, use A1 liquid and polycarbonate resin, reach and use B liquid or C liquid as required, be mixed into the composition shown in the sample 2～10 of following table 1 respectively, make the whole homodisperse hot radiation shielding polycarbonate resin sheets of hot radiation shielding particulate (test portion 2～10).
Each hot radiation shielding polycarbonate sheet to the test portion 1～10 that makes, use the spectrophotometer U-4000 of Hitachi's system to measure dichroism respectively, calculate visible light transmissivity according to JIS R3106, with the sunlight transmitance of expression hot radiation shielding performance, the following table 1 that the results are shown in that obtains.
Comparative example 1
Adopt method similarly to Example 1, but do not use A1 liquid, B1 liquid or C1 liquid and polycarbonate resin are mixed into the composition shown in the sample 11～12 of table 1 as described below, make the whole homodisperse hot radiation shielding polycarbonate sheets of ITO or ATO particulate (test portion 11～12).The hot radiation shielding polycarbonate sheet to these, the result who also estimates similarly to Example 1 is shown in following table 1 together.
Embodiment 2
Hot radiation shielding polycarbonate sheet (LaB at the test portion 2 of the foregoing description 1
6Use with ITO) the surface form the ultraviolet radiation absorption film.That is be benzotriazole that (vapour crust fine chemicals company (チ バ ス ペ シ ヤ リ テ イ one) system: trade(brand)name Tinuvin (チ ヌ PVC Application) 384) 2 weight %, acrylic resin 10 weight parts, toluene 88 weight parts mix ultraviolet vapor, make coating fluid.Use spin coater that this coating fluid 15g is coated on the sheet material of sample 2, the electric furnace heating of putting into 100 ℃ formed the ultraviolet radiation absorption film in 30 minutes.
To the hot radiation shielding polycarbonate sheet (test portion 13) of the band ultraviolet radiation absorption film that obtains, also estimate similarly to Example 1, evaluation result is shown in following table 1.
Comparative example 2
Adopt the method same, A1 liquid, C1 liquid, polycarbonate resin are mixed into the composition shown in the test portion 14 of following table 1, make the whole homodisperse hot radiation shielding polycarbonate sheets of hot radiation shielding particulate (test portion 14) with the foregoing description 1.
The hot radiation shielding polycarbonate sheet of the test portion 14 that makes because the amount of hot radiation shielding particulate is too many, is separated out the hot radiation shielding composition so find the surface, and sheet material all is white in color dizzy turbid.The hot radiation shielding polycarbonate sheet to this test portion 14, the result who also estimates similarly to Example 1 is shown in following table 1 together.
[table 1]
| Test portion | The hot radiation shielding sheet material is formed (wt%) | Total particulate loading (g/m 2) | Visible light transmissivity (%) | Sunlight transmitance (%) | ||
| ????LaB 6 | ????ITO | ??ATO | ||||
| ????1 | ????0.00097 | ????0.155 | ????0 | ????5.79 | ????78 | ????55.6 |
| ????2 | ????0.0013 | ????0.092 | ????0 | ????3.36 | ????78 | ????54.2 |
| ????3 | ????0.0018 | ????0.082 | ????0 | ????3.02 | ????78 | ????54.7 |
| ????4 | ????0.0022 | ????0.067 | ????0 | ????2.49 | ????78 | ????57.5 |
| ????5 | ????0.0035 | ????0.030 | ????0 | ????1.20 | ????78 | ????59.3 |
| ????6 | ????0.0050 | ????0 | ????0 | ????0.18 | ????78 | ????59.7 |
| ????7 | ????0.00097 | ????0 | ????0.51 | ????18.70 | ????78 | ????62.5 |
| ????8 | ????0.0028 | ????0 | ????0.27 | ????9.82 | ????78 | ????61.3 |
| ????9 | ????0.0040 | ????0 | ????0.20 | ????7.34 | ????78 | ????61.0 |
| ????10 | ????0.0042 | ????0 | ????0.15 | ????5.55 | ????78 | ????62.0 |
| ????11 * | ????0 | ????0.18 | ????0 | ????648 | ????78 | ????57.8 |
| ????12 * | ????0 | ????0 | ????0.61 | ????21.96 | ????78 | ????63.1 |
| ????13 * | ????0.0013 | ????0.092 | ????0 | ????3.36 | ????77 | ????54.2 |
| ????14 * | ????0.0020 | ????0 | ????0.70 | ????25.27 | ????52 | ????38.1 |
Band in (notes) table
*Number test portion be comparative example.
Result by above-mentioned table 1 finds out, by the LaB of trace interpolation as the hot radiation shielding composition
6, visible light transmissivity is low unlike the characteristic of the ITO in past or ATO, can make the sunlight transmitance identical or reduce to lower degree.Even and find out and do not add ITO or ATO also can obtain this effect, in addition, and can reduce the addition of particulate significantly with the occasion of ITO or ATO.
For example, when the test portion 11 of the test portion 2 of example of the present invention and comparative example is compared, in the sheet material of test portion 2 owing to added 1.39 weight %LaB of total particulate in the film
6So visible light transmissivity still maintains 78%, and the sunlight transmitance has been reduced more than 3 percentage points or 3 percentage points than test portion 11.In addition, can make the addition of ITO reduce to half or half below.
Embodiment 3
Hot radiation shielding polycarbonate sheet to the test portion 4 of the foregoing description 1 is implemented water tolerance test.That is, the sheet material of test portion 4 flooded 10 days in water after, measure optical characteristics similarly to Example 1 again, visible light transmissivity is 78% as a result, the sunlight transmitance is 57.5%, does not occur change of optical property fully.
Embodiment 4
The CeB of median size 85nm
6Particulate 20g, toluene 70g, water and an amount of dispersion agent mix, and use the zirconia ball of diameter 4mm to carry out ball mill mixing in 100 hours, make annex solution (D1 liquid) 100g.Adopt the method same, D1 liquid, B1 liquid, polycarbonate resin are mixed into the composition shown in the test portion 15 of following table 2, make the whole homodisperse hot radiation shielding polycarbonate sheets of hot radiation shielding particulate (test portion 15) with the foregoing description 1.
In addition, use PrB
6Particulate, NdB
6Particulate, GdB
6Particulate, YB
6Particulate, SmB
6Particulate or EuB
6Particulate replaces above-mentioned CeB
6Particulate is with the above-mentioned annex solution that similarly makes respectively.These annex solution and polycarbonate resin, and be mixed into the composition shown in the test portion 16～21 of above-mentioned table 2 with B1 liquid or C1 liquid as required, make the whole homodisperse hot radiation shielding polycarbonate sheets of hot radiation shielding particulate (test portion 16～21).
Each the hot radiation shielding polycarbonate sheet to gained test portion 15～21, that estimates similarly to Example 1 the results are shown in following table 2.
[table 2]
| Test portion | The hot radiation shielding sheet material is formed (wt%) | Total particulate loading (g/m 2) | Visible light transmissivity (%) | Sunlight transmitance (%) | ||
| Hexaboride | ????ITO | ????ATO | ||||
| ????15 | ?CeB 6/0.0020 | ????0.083 | ????0 | ????3.06 | ????77 | ????53.8 |
| ????16 | ?PrB 6/0.0022 | ????0.080 | ????0 | ????2.96 | ????77 | ????54.1 |
| ????17 | ?NdB 6/0.0028 | ????0 | ????0.27 | ????9.82 | ????78 | ????62.1 |
| ????18 | ?GdB 6/0.0027 | ????0 | ????0.29 | ????10.53 | ????78 | ????61.9 |
| ????19 | ?YB 6/0.0018 | ????0.073 | ????0 | ????2.69 | ????78 | ????54.0 |
| ????20 | ?SmB 6/0.0040 | ????0 | ????0.20 | ????7.34 | ????77 | ????61.5 |
| ????21 | ?EuB 6/0.0040 | ????0 | ????0.18 | ????6.62 | ????77 | ????61.8 |
Find out thus, use CeB
6Particulate, PrB
6Particulate, NdB
6Particulate, GdB
6Particulate, YB
6Particulate, SmB
6Particulate, EuB
6The hexaboride particulate of particulate etc. replaces the LaB as the hot radiation shielding composition
6Particulate also can obtain excellent visible light perviousness and hot radiation shielding effect.
Embodiment 5
The LaB of median size 67nm
6Particulate 20g, toluene 70g, water and an amount of dispersant, the zirconia ball of use diameter 4mm carries out 100 hours ball mills and mixes, and makes annex solution (A2 liquid) 100g.In addition,, similarly carry out ball mill and mix, make annex solution (B2 liquid) 100g ITO particulate 20g, toluene 70g, water and an amount of dispersant of median size 80nm.ATO particulate 20g, toluene 70g, water and an amount of dispersant of median size 55nm, similarly carry out ball mill and mix again, make annex solution (C2 liquid) 100g.
Then, above-mentioned A2 liquid and B2 liquid are carried out mixing preparation acrylic resin annex solution, this annex solution is added to make ITO concentration in the acrylic resin be 0.13 weight %, LaB
6Concentration is 0.0012 weight %, use mixing roll, twin screw extruder evenly to carry out melting mixing after, use T pattern head to carry out extrusion moulding and make thickness and be 3mm, make the whole homodisperse hot radiation shielding vinylformic acid sheet materials of hot radiation shielding particulate (test portion 22).
Adopt and above-mentioned same method, use A2 liquid and acrylic resin, reach and use B2 liquid or C2 liquid as required, be mixed into the composition shown in the test portion 23～31 of following table 3, make the whole homodisperse hot radiation shielding vinylformic acid sheet materials of hot radiation shielding particulate (test portion 23～31).
Each hot radiation shielding acrylic resin sheet material to the test portion 22～31 that makes, use the spectrophotometer U-4000 of Hitachi's system to measure dichroism respectively, calculate visible light transmissivity according to JIS R3106, sunlight transmitance with expression hot radiation shielding performance the results are shown in following table 3 to gained.
Comparative example 3
Adopt the method same with the foregoing description 5, but do not use A2 liquid, B2 liquid or C2 liquid and acrylic resin are mixed into the composition shown in the test portion 32～33 of following table 3, make the whole homodisperse hot radiation shielding acrylic resin sheet materials of hot radiation shielding particulate (test portion 32～33).The result that these hot radiation shielding acrylic resin sheet material is also estimated similarly to Example 5 is shown in following table 3 together.
Embodiment 6
The A2 liquid of the foregoing description 5 and B2 liquid blended annex solution added to make ITO concentration in the acrylic resin be 0.094 weight %, LaB
6Concentration is 0.0012 weight %, after the even melting mixing of use mixing roll, is 3mm by using the extrusion moulding of T pattern head to make thickness, makes the whole homodisperse hot radiation shielding acrylic resin sheet materials of hot radiation shielding particulate.
Use spin coater, on a surface of this hot radiation shielding acrylic resin sheet material, the coating benzotriazole is that (vapour crust fine chemicals corporate system: trade(brand)name Tinuvin) 2 weight %, acrylic resin 10 weight parts, toluene 88 weight part blended coating fluid 15g, the electric furnace heating of putting into 100 ℃ formed the ultraviolet radiation absorption film in 30 minutes to UV light absorber.
To hot radiation shielding polycarbonate (the Port リ カ one ボ ネ one ト) sheet material (test portion 34) of the band ultraviolet radiation absorption film that obtains, estimate similarly to Example 5, evaluation result is shown in following table 3.
Comparative example 4
Adopt the method same, A2 liquid, C2 liquid, acrylic resin are mixed into the composition shown in the test portion 35 of following table 3, make the whole homodisperse hot radiation shielding acrylic resin sheet materials of hot radiation shielding particulate (test portion 35) with the foregoing description 5.
The hot radiation shielding acrylic resin sheet material of prepared test portion 35, because the amount of hot radiation shielding composition is too many, so separating out of hot radiation shielding composition appears in the surface, sheet material all is white in color dizzy turbid.The result that the hot radiation shielding acrylic resin sheet material of this test portion 35 is also estimated similarly to Example 5 is shown in following table 3 together.
[table 3]
| Test portion | The hot radiation shielding sheet material is formed (wt%) | Total particulate loading (g/m 2) | Visible light is crossed rate (%) | Sunlight transmitance (%) | ||
| ??LaB 6 | ????ITO | ????ATO | ||||
| ????22 | ????0.0012 | ????0.13 | ????0 | ????4.72 | ????78 | ????55.3 |
| ????23 | ????0.0016 | ????0.077 | ????0 | ????2.83 | ????78 | ????54.5 |
| ????24 | ????0.0022 | ????0.068 | ????0 | ????2.53 | ????78 | ????54.9 |
| ????25 | ????0.0026 | ????0.056 | ????0 | ????2.11 | ????78 | ????56.9 |
| ????26 | ????0.0042 | ????0.025 | ????0 | ????1.05 | ????78 | ????59.3 |
| ????27 | ????0.0049 | ????0 | ????0 | ????0.18 | ????78 | ????59.8 |
| ????28 | ????0.0011 | ????0 | ????0.46 | ????16.60 | ????78 | ????62.9 |
| ????29 | ????0.0031 | ????0 | ????0.25 | ????9.11 | ????78 | ????62.4 |
| ????30 | ????0.0044 | ????0 | ????0.18 | ????6.63 | ????78 | ????61.5 |
| ????31 | ????0.0046 | ????0 | ????0.14 | ????5.20 | ????78 | ????62.9 |
| ????32 * | ????0 | ????0.18 | ????0 | ????6.48 | ????78 | ????57.3 |
| ????33 * | ????0 | ????0 | ????0.60 | ????21.60 | ????78 | ????64.9 |
| ????34 | ????0.0012 | ????0.094 | ????0 | ????3.43 | ????77 | ????55.0 |
| ????35 * | ????0.0019 | ????0 | ????0.74 | ????26.71 | ????51 | ????37.1 |
Band in (notes) table
*Number test portion be comparative example.
Result by above-mentioned table 3 finds out, by the micro-LaB that adds as the hot radiation shielding composition in acrylic resin
6, compare with the ITO in past or the characteristic of ATO, do not reduce visible light transmissivity, and can make the sunlight transmitance identical or reduce to lower.And, even also find out and do not add ITO or ATO also can obtain this effect, can reduce significantly in addition and with its addition of occasion of ITO or ATO.
For example,, then find out the sheet material of test portion 23, by adding 2.03 weight %LaB of total particulate in the film if the test portion 23 of example of the present invention and the test portion 32 of comparative example are compared
6Particulate, then visible light transmissivity still maintains 78%, makes the sunlight transmitance reduce about 3 percentage points than the test portion 32 of comparative example, the ITO addition can be reduced to again half or half below.
Embodiment 7
Hot radiation shielding acrylic resin sheet material to the test portion 25 of the foregoing description 5 is implemented water tolerance test.That is, the sheet material of sample 25 flooded 10 days in water after, measure optical characteristics similarly to Example 1 again, visible light transmissivity is 78% as a result, and the sunlight transmitance is 56.9%, does not find change of optical property fully.
Embodiment 8
The CeB of flat footpath particle diameter 85nm
6Particulate 20g, toluene 70g, water and an amount of dispersant use the zirconia ball of diameter 4mm to carry out ball mill mixing in 100 hours, make annex solution (D2 liquid) 100g.Adopt the method same, D2 liquid, B2 liquid, acrylic resin are mixed into the composition shown in the test portion 36 of following table 4, make the whole homodisperse hot radiation shielding acrylic resin sheet materials of hot radiation shielding particulate (test portion 36) with the foregoing description 5.
In addition, use PrB
6Particulate, NdB
6Particulate, GdB
6Particulate, YB
6Particulate, SmB
6Particulate, EuB
6Particulate replaces above-mentioned CeB
6Particulate is with the above-mentioned annex solution that similarly makes respectively.These annex solution and acrylic resin, and be mixed into the composition shown in the test portion 37～42 of following table 4 with B2 liquid or C2 liquid as required, make the whole homodisperse hot radiation shielding acrylic resin sheet materials of hot radiation shielding particulate (test portion 37～42).
Each the hot radiation shielding acrylic resin sheet material to gained test portion 36～42, that estimates similarly to Example 5 the results are shown in following table 4.
[table 4]
| Test portion | The hot radiation shielding sheet material is formed (wt%) | Total particulate loading (g/m 2) | Visible light transmissivity (%) | Sunlight transmitance (%) | ||
| Hexaboride | ????ITO | ????ATO | ||||
| ????36 | ?CeB 6/0.0020 | ????0.085 | ????0 | ????3.13 | ????77 | ????53.3 |
| ????37 | ?PrB 6/0.0022 | ????0.081 | ????0 | ????3.00 | ????77 | ????55.1 |
| ????38 | ?NdB 6/0.0030 | ????0 | ????0.26 | ????9.47 | ????78 | ????63.4 |
| ????39 | ?GdB 6/0.0030 | ????0 | ????0.28 | ????10.19 | ????78 | ????61.9 |
| ????40 | ?YB 6/0.0018 | ????0.073 | ????0 | ????2.69 | ????78 | ????53.7 |
| ????41 | ?SmB 6/0.0039 | ????0 | ????0.21 | ????7.70 | ????77 | ????62.0 |
| ????42 | ?EuB 6/0.0039 | ????0 | ????0.18 | ????6.62 | ????77 | ????62.1 |
Embodiment 9
To hot radiation shielding polycarbonate sheet, the hot radiation shielding of test portion 10 in the foregoing description 1 become the too much test portion of component 14 the hot radiation shielding polycarbonate sheet, and do not contain the polycarbonate sheet (test portion 43) of hot radiation shielding composition, carry out the mensuration of Izod impact strength respectively according to ASTM D-256 (v-notch).The results are shown in following table 5 resulting.
[table 5]
| Test portion | Total particulate loading (g/m 2) | Shock strength (kgcmcm -1) |
| ????10 | ????5.55 | ????77 |
| ????14 * | ????25.27 | ????35 |
| ????43 * | ????0 | ????78 |
Band in (notes) table
*Number test portion be comparative example.
Find out that by table the hot radiation shielding polycarbonate sheet of test portion 10 of the present invention has the equal shock-resistance of polycarbonate sheet that does not contain the hot radiation shielding composition with test portion 43.But hot radiation shielding as a comparative example becomes the hot radiation shielding polycarbonate sheet of the too much test portion of component 14, and shock-resistance reduces significantly than above-mentioned test portion 10 and test portion 43.
Industrial applicibility
If adopt physical film deposition method that the present invention then need not be expensive or numerous and diverse bonding process, the hexaboride particulate is dispersed in this short-cut method in the resin makes, and can provide and have high hot radiation shielding function, simultaneously visible domain had excellent diactinic hot radiation shielding resin sheet and can adopt. And this hot radiation shielding resin sheet is because the hexaboride microparticulate wraps in the resin, so intercept the contacting of hexaboride particulate and water, resistance to water.
In addition; by using the infrared territory of pairing approximation that the hexaboride particulate of strong absorption is arranged; use a small amount of hot radiation shielding composition then can obtain high hot radiation shielding effect, even also can reduce its use amount when using with ATO particulate or ITO particulate, can reduce Master Cost. Again, but because total particulate loading of decrease hot radiation shielding composition, so can prevent reduction as the physical property of the resin of base material, especially impact strength or toughness.
Therefore, hot radiation shielding resin sheet of the present invention is by being used for the opening portion of building or automotive window and so on, owing to can shield the solar energy that enters from peristome, so have the hot summer weather sense that alleviates between refrigeration load or people, consider also extremely useful from energy-conservation viewpoint.
Claims (11)
1. a hot radiation shielding resin sheet is characterized in that, in transparent resin base material, disperses the hexaboride particulate or disperses hexaboride particulate and ITO particulate and/or ATO particulate, as the hot radiation shielding composition.
2. the described hot radiation shielding resin sheet of claim 1 is characterized in that aforementioned hexaboride is to be selected from LaB
6, CeB
6, PrB
6, NdB
6, GdB
6, TbB
6, DyB
6, HoB
6, YB
6, SmB
6, EuB
6, ErB
6, TmB
6, YbB
6, LuB
6, SrB
6And CaB
6In at least a kind.
3. claim 1 or 2 described hot radiation shielding resin sheets is characterized in that, aforementioned hexaboride particulate, ITO particulate and ATO particulate, and its median size all is 200nm or below the 200nm.
4. the described hot radiation shielding resin sheet of any one of claim 1～3 is characterized in that, the content of aforementioned hot radiation shielding composition is every 1m
2The hot radiation shielding resin sheet is 0.05～19g.
5. the described hot radiation shielding resin sheet of any one of claim 1～4 is characterized in that, the ratio of aforementioned hexaboride particulate and ITO particulate and/or ATO particulate is 0.1: 99.9～90: 10 scope by weight.
6. the described hot radiation shielding resin sheet of any one of claim 1～5 is characterized in that the aforementioned resin base material comprises polycarbonate resin or acrylic resin.
7. the described hot radiation shielding resin sheet of any one of claim 1～6 is characterized in that, forms the resin coating that contains UV light absorber at least one surface of this hot radiation shielding resin sheet.
8. hot radiation shielding resin sheet manufacturing annex solution, this annex solution is the annex solution that is mixed into hot radiation shielding resin sheet molding composition with resin or resin raw material, it is characterized in that, in solvent, disperse hexaboride particulate, or disperse hexaboride particulate and ITO particulate and/or ATO particulate as the hot radiation shielding composition.
9. the described hot radiation shielding resin sheet of claim 8 manufacturing annex solution is characterized in that aforementioned hexaboride is to be selected from LaB
6, CeB
6, PrB
6, NdB
6, GdB
6, TbB
6, DyB
6, HoB
6, YB
6, SmB
6, EuB
6, ErB
6, TmB
6, YbB
6, LuB
6, SrB
6And CaB
6In at least a kind.
10. claim 8 or 9 described hot radiation shielding resin sheet manufacturing annex solutions is characterized in that, aforementioned hexaboride particulate, ITO particulate and ATO particulate, and its median size all is 200nm or below the 200nm.
11. the described hot radiation shielding resin sheet of any one of claim 8～10 manufacturing annex solution is characterized in that, the ratio of aforementioned hexaboride particulate and ITO particulate and/or ATO particulate is 0.1: 99.9～90: 10 scope by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002136457A JP4187999B2 (en) | 2002-05-13 | 2002-05-13 | Heat ray shielding resin sheet material and manufacturing method thereof |
| JP136457/2002 | 2002-05-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1639265A true CN1639265A (en) | 2005-07-13 |
| CN1329451C CN1329451C (en) | 2007-08-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038054124A Expired - Fee Related CN1329451C (en) | 2002-05-13 | 2003-05-07 | Heat ray shielding sheet material and liquid additive for use in producing the same |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9074071B2 (en) |
| JP (1) | JP4187999B2 (en) |
| KR (1) | KR100644012B1 (en) |
| CN (1) | CN1329451C (en) |
| AU (1) | AU2003235856B2 (en) |
| DE (1) | DE10392543T5 (en) |
| IN (1) | IN2004DE02187A (en) |
| WO (1) | WO2003095561A1 (en) |
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-
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- 2002-05-13 JP JP2002136457A patent/JP4187999B2/en not_active Expired - Lifetime
-
2003
- 2003-05-07 DE DE10392543T patent/DE10392543T5/en not_active Withdrawn
- 2003-05-07 AU AU2003235856A patent/AU2003235856B2/en not_active Ceased
- 2003-05-07 CN CNB038054124A patent/CN1329451C/en not_active Expired - Fee Related
- 2003-05-07 US US10/480,940 patent/US9074071B2/en not_active Expired - Fee Related
- 2003-05-07 KR KR20047015670A patent/KR100644012B1/en active IP Right Grant
- 2003-05-07 WO PCT/JP2003/005673 patent/WO2003095561A1/en active Application Filing
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2004
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|---|---|---|---|---|
| CN101421353B (en) * | 2006-04-14 | 2012-06-06 | 出光兴产株式会社 | Polycarbonate resin composition and molded plate thereof |
| CN101522801B (en) * | 2006-12-21 | 2011-11-02 | 帝人化成株式会社 | Polycarbonate resin composition and molded article thereof |
| CN101070442B (en) * | 2007-06-06 | 2010-08-25 | 长兴科技(上海)有限公司 | Composite material and composition containing same |
| CN104371281A (en) * | 2013-08-13 | 2015-02-25 | 台虹科技股份有限公司 | Light absorbing and heat accumulating composition and light absorbing and heat accumulating structure prepared therefrom |
| CN114902510A (en) * | 2019-12-19 | 2022-08-12 | 烙克赛克有限公司 | Transfer device for passing at least one cable and/or at least one metal pipe |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4187999B2 (en) | 2008-11-26 |
| KR100644012B1 (en) | 2006-11-10 |
| US9074071B2 (en) | 2015-07-07 |
| JP2003327717A (en) | 2003-11-19 |
| IN2004DE02187A (en) | 2007-04-06 |
| DE10392543T5 (en) | 2005-04-07 |
| WO2003095561A1 (en) | 2003-11-20 |
| CN1329451C (en) | 2007-08-01 |
| AU2003235856B2 (en) | 2009-01-29 |
| KR20050006137A (en) | 2005-01-15 |
| AU2003235856A1 (en) | 2003-11-11 |
| US20040131845A1 (en) | 2004-07-08 |
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